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EP1678259A2 - Disperse azo dyestuffs - Google Patents

Disperse azo dyestuffs

Info

Publication number
EP1678259A2
EP1678259A2 EP04790444A EP04790444A EP1678259A2 EP 1678259 A2 EP1678259 A2 EP 1678259A2 EP 04790444 A EP04790444 A EP 04790444A EP 04790444 A EP04790444 A EP 04790444A EP 1678259 A2 EP1678259 A2 EP 1678259A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
hydrogen
formula
group
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP04790444A
Other languages
German (de)
French (fr)
Other versions
EP1678259B1 (en
Inventor
Nigel Hall
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dystar Colours Distribution GmbH
Original Assignee
Dystar Textilfarben GmbH and Co Deutschland KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dystar Textilfarben GmbH and Co Deutschland KG filed Critical Dystar Textilfarben GmbH and Co Deutschland KG
Publication of EP1678259A2 publication Critical patent/EP1678259A2/en
Application granted granted Critical
Publication of EP1678259B1 publication Critical patent/EP1678259B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
    • C09B29/0815—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by -C(=O)-
    • C09B29/0816—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by -C(=O)- substituted by -COOR
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/04—Disazo dyes from a coupling component "C" containing a directive amino group
    • C09B31/043—Amino-benzenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber

Definitions

  • the present invention relates to the field of disperse dyes.
  • Disperse dyestuffs containing cyanomethyl ester groups are known from literature and are described for example in GB 909,843, DE-A 2130992, GB 1 ,457,532, GB 1 ,536,429, FR-A 1 ,531 , 147, US 3,776,898, JP 551 61 857, GB 2, 1 04,088, EP 0 685 531 A1 and WO 95/20014.
  • the inventor of the present invention has surprisingly found that dyeings on polyester with very good wet fastness properties can be obtained if selected dyestuffs containing one cyanomethylester group as defined below are used.
  • the present invention claims dyestuffs of the formula I
  • T ⁇ T 2 and T 3 are, independently, hydrogen, halogen or nitro; T 4 is hydrogen, halogen, cyano or nitro; wherein at least one of T ⁇ T 2 , T 3 and T 4 is not hydrogen; or a group of the formula (lib)
  • T 5 is hydrogen or halogen; and T 6 is hydrogen -SO 2 CH 3 , -SCN or nitro; wherein at least one of T 5 and T 6 is not hydrogen; or a group of the formula (lie)
  • T 7 is nitro, -CHO or a group of the formula
  • T is -H, halogen, nitro and cyano; T 8 is hydrogen or halogen; and T 9 is nitro, cyano, -COCH 3 or -COOT 10 , wherein T 10 is (C,-C 4 )-alkyl; or a group of the formula (lie)
  • R 1 is hydrogen, (C C 4 )-alkyl or -NCOR 6 , where R 6 is (C,-C 4 )-alkyl or phenyl;
  • R 2 is unsubstituted (C,-C 6 )-alkyl, substituted (C C 6 )-alkyl, benzyl or phenylethyl;
  • R 3 is hydrogen or methyl;
  • R 4 is hydrogen or methyl;
  • R 5 is hydrogen, methyl or phenyl;
  • R 7 is hydrogen, chloro, methoxy or ethoxy; n is 0, 1 or 2; s is 0 or 1 ;
  • D is a group of the formula (lie), (lid), (lie) or (lla) wherein T 1 is not nitro if T 2 , T 3 and T 4 are hydrogen, - if T 2 and T 3 are hydrogen and T 4 is chlorine or cyano and if T 2 and T 4 are hydrogen and T 3 is chlorine; and
  • Alkyl groups standing for R 1 , R 6 or T 10 may be straight-chain or branched and are preferably methyl, ethyl, n-propyl, i-propyl or n-butyl. The same applies to alkyl groups standing for R 2 , which can in addition be pentyl or hexyl. Substituted alkyl groups standing for R 2 are preferably substituted by hydroxyl, (C C 4 )-alkoxy or halogen. Halogen standing for T ⁇ T 2 , T 3 , T 4 , T 5 or T 8 are preferably chlorine or bromine.
  • D derive from the following amines: 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-chloro-4-nitroaniline, 4-chloro-2- nitroaniline, 2-bromo-4-nitroaniIine, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4- nitroaniline, 2-ch oro-6-bromo-4-nitroaniline, 2,5-dichloro-4-nitroaniline, 2-cyano- 4-nitroaniline, 2-cyano-6-bromo-4-nitroaniline, 2-cyano-6-ch!oro-4-nitroaniline, 2,4-dinitroaniIine, 2-chloro-4,6-dinitroaniIine, 2-bromo-4,6-dinitroaniline, 2,6- dicyano-4-nitroaniIine, 2-cyano-4,6-dinitroaniline, 2-amino-5-nitrothiazole, 2- amino-3,5-dinitrothiophene, 2-amino-3-ethoxycarbon
  • 10 D is a group of the formulae (Ha), (lib), (lie), (lid) or (lie); R 1 is (C C 4 )-alkyl; R 2 is unsubstituted (C C 6 )-alkyl, benzyl or phenylethyl; and n is 0, 1 or 2.
  • R 2 is unsubstituted (C C 6 )-alkyl, substituted (C C 6 )-alkyl, benzyl or phenylethyl; 25
  • R 2 is ethyl, benzyl or phenethyl.
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (lc)
  • D is a group of the formulae (lla), (lib), (lie), (ild) or (lie);
  • R 1 is hydrogen, (C r C 4 )-alkyl or -NCOR 6 , where R 6 is (C r C 4 )-alkyl or phenyl;
  • R 2 is unsubstituted (C r C 6 )-alkyl, substituted (C r C 6 )-alkyI, benzyl or phenylethyl;
  • R 3 is hydrogen and R is methyl or R 3 is methyl and R is hydrogen.
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (Id)
  • D is a group of the formulae (lla), (lib), (lie), (Ild) or (lie);
  • R 1 is hydrogen, (C r C 4 )-alkyl or -NCOR 6 , where R 6 is (C C 4 ) -alkyl or phenyl;
  • R 2 is unsubstituted (C C 6 )-alkyl, substituted (C C 6 ) -al yl, benzyl or phenylethyl;
  • R 5 is methyl or phenyl
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (le)
  • D is a group of the formulae (lla), (lib), (lie), (Ild) or (lie);
  • R 2 is unsubstituted (C C 6 )-alkyl, substituted (C r C 6 )-alkyl, benzyl or phenylethyl;
  • R 6 is (C r C 4 )-aIkyl or phenyl;
  • R 7 is chloro, methoxy or ethoxy; and n is 0, 1 or 2.
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (If)
  • R 2 is unsubstituted (C C 6 )-aikyl, substituted (C C 6 )-alkyl, benzyl or phenylethyl; R 8 is nitro; and n is 0, 1 or 2;
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ig)
  • D is a group of the formulae (lla), (Mb), (He), (lid) or (lie);
  • R 1 is hydrogen, (C C 4 )-alkyi or -NCOR 6 , where R 6 is (C r C 4 )-alkyi or phenyl;
  • R 2 is unsubstituted (C,-C 6 )-alkyl, substituted (C C 6 )-alkyl, benzyl or phenylethyl; and R 3 is hydrogen or methyl.
  • the compounds of the formula I may be obtained by usual methods for the preparation of azo compounds such as by diazbtisation of an amine of the formula III D-NH 2 (III) wherein D is defined as given above, and coupling onto a compound of the formula IV
  • R ⁇ R 2 , R 3 , R 4 , R 5 and R 7 are defined as given above.
  • the amine of the formula (III) may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from -1 0°C to 1 0°C.
  • a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from -1 0°C to 1 0°C.
  • Coupling onto the compound of the formula (IV) may be achieved by adding the diazotised amine to the compound of the formula (IV) under conditions described in literature and known to the skilled persons.
  • the compounds of the formula (I) are useful for dyeing and printing of synthetic textile material particularly polyester textile materials and fibre blends thereof with for example cellulosic materials like cotton, to which they impart colours Y which have excellent wet fastness properties.
  • Dyeing of the fibre goods mentioned with the dyestuffs of the formula (I) can be carried out in a manner known per se, preferably from aqueous dispersions, if appropriate in the presence of carriers, at between 80 and 1 1 0°C, by the exhaust process or by the HT process in a dyeing autoclave at 1 1 0 to 1 40°C, and by the so-called thermofixing process, in which the goods are padded with the dye liquor and then fixed at about 1 80 to 230°C.
  • the fibre goods mentioned can as well be printed in a manner known pers e by a procedure in which the dyestuffs of the formula (I) are incorporated into a printing paste and the goods printed with the paste are treated , if appropriate in the presence of a carrier, with HT steam, pressurized steam or dry heat at temperatures between 180 and 230°C to fix the dyestuff.
  • the dyestuffs of the formula (I) should be present in the finest possible dispersion in the dye liquors and printing pastes employed in the above applications.
  • the fine dispersion of the dyestuffs is effected in a manner known per se by a procedure in which the dyestuff obtained during preparation is suspended ina liquid medium, preferably in water, together with dispersing agents and the mixture is exposed to the action of shearing forces, the particles originally present being comminuted mechanically to the extent that an optimum specific surface area is achieved and sedimentation of the dyestuff is as low as possible.
  • the particle size of the dyestuffs is in general between 0.5 and 5 m, preferably about 1 m.
  • the dispersing agents used can be nonionic or anionic.
  • Nononic dispersing agents are, for example, reaction products of alkylene oxides, such as, for example, ethylene oxide or propyiene oxide, with alkylatable compounds, such as for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines.
  • alkylatable compounds such as for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines.
  • Anionic dispersing agnets are, for example, lignin- sulphonates, alkyl- or alkylarylsulphonates or alkylaryl polyglycol ethersulphates.
  • the dyestuff formulations thus obtained should be The dyestuff and dispersing agent content is therefore limited in these cases.
  • the dispersions are brought to a dyestuff content of up to 50 per cent by weight and a dispersing agent content of up to 25 per cent by weight.
  • the dyestuff contents usually do not fall below 1 5 per cent by weight.
  • the dispersions can also comprise other auxiliaries, for example those which act as oxidizing agents or fungicidal agents. Such agents are well known in the art.
  • the dyestuff dispersion thus obtained can be used very advantageously for the preparation of printing pastes and dye liquors.
  • powder formulations are preferred. These powders comprise the dyestuff, dispersing agents and other auxiliaries, such as, for example, wetting agents, oxidizing agents, preservatives and dust removal agents.
  • a preferred preparation process for pulverulent dyestuff formulations comprises removing the liquid from the liquid dyestuff dispersions described above, for example by vacuum drying, freeze drying, by drying on roller dryers, but preferably by spray drying.
  • 2-amino-6-nitrobenzothiazole (3.9parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (40parts). Nitrosyl sulrlhuric acid 40% (7.6parts) was added below 5°C and the mixture was stirred for 1 hour. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (5.9parts), methanol (25parts), water (200parts) and sulphamic acid (0.5parts).
  • Example 80 were prepared by the procedure of Example 80 (see Table 3)
  • Example 1 4-(3,5-dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline
  • 2-amino-3,5-dinitrothiophene (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (50parts) .
  • Nitrosyl sulphuric acid 40% (5.7parts) was added below 5°C and the mixture was stirred for 30 mins.
  • the diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonyethyl)-m-toluidine (4.0parts), acetone (50parts), water (300parts) and sulphamic acid (O. ⁇ parts) .
  • Example 1 27 4-(5-nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N-(2- cyanomethoxycarbonyiethyl) aniline
  • Example 1 27 were prepared by the procedure of Example 1 27 (see Table 5)
  • 2-amino-5-nitrothiazole (2.9parts) was was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (50parts). Nitrosyl sulphuric acid 40% (7.0parts) was added below 5°C and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-butyl, N-2(cyanomethoxycarbonylethyl)-aniline ( ⁇ .2parts), acetone ( ⁇ Oparts), water (200parts) and sulphamic acid (O. ⁇ parts).
  • Example 1 39 4 (2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2- cyanomethoxycarbonylethyD-aniline
  • 2-chloro-4-nitroaniline (3. ⁇ parts) was set stirring at ⁇ °C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (7.0parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of 3(N- ethyl, N-cyanomethoxycarbonylethyl)-amino-acetanilide (6.3parts), methanol (40parts), water (200parts) and sulphamic acid O part).
  • Example139 were prepared by the procedure of Example139 (see Table 7)
  • 2-cyano-4-nitroaniline (3.2part,s) was set stirring at ⁇ °C with a mixture of acetic acid and propionic acid, 86:14s( ⁇ 0parts). Nitrosyl sulphuric acid 40% (7.6parts) was added below ⁇ °C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(4-cyanomethoxycarbonylbutyl)-m-toluidine ( ⁇ .Oparts), methanol ( ⁇ Oparts), water (200parts) and sulphamic acid part).
  • Example 1 69 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1 -cyanoethoxy) carbonylethyD-aniline
  • 2-cyano-4-nitroaniline (2.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (40parts). Nitrosyl sulphuric acid 40% (4.9parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1 -cyanoethoxy)carbonylethyl)-m-toluidine (3.7parts), acetone ( ⁇ Oparts), water (300parts) and sulphamic acid O part).
  • Example169 were prepared by the procedure of Example169 (see Table 9)
  • 2-chloro-4-nitr ⁇ a;hiline (parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (40parts). Nitrosyl sulphuric acid 40% (4.9parts) was added below ⁇ °C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2-(cyanomethoxycarbonylpropyl)-aniline (parts), acetone ( ⁇ Oparts), water (300parts) and sulphamic acid O part).
  • Example194 were prepared by the procedure of Example194 (see Table 10)
  • Example 21 3 4-(4-nitrophenylazo)-N-ethyl-N-(2-( 1 -cyanoethoxy) carbonylpropyD-aniline
  • 4-nitroaniline (2.0parts) was set stirring at ⁇ °C with a mixture of acetic acid and propionic acid, 86: 14 ( ⁇ Oparts). Nitrosyl sulphuric acid 40% ( ⁇ .7parts) was added below ⁇ °C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1 -cyanoethoxy)carbonylpropyl)-aniline (4.7parts), acetone ( ⁇ Oparts), water (200parts) and sulphamic acid O part) .
  • 2-cyano-4-nitroaniline (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (40parts). Nitrosyl sulphuric acid 40% (6.6parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-0 -cyanomethoxycarbonylethyl)-m-toluidine (4.1 parts), methanol (40parts), water (200parts) and sulphamic acid O part).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Ink Jet (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention claims dyestuffs of formula (I), wherein D, R1 to R7 and n are defined as given in claim 1, a process for their preparation and their use.

Description

DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG 2003/C 004 Dr. My
Description
Disperse Azo Dyestuffs
The present invention relates to the field of disperse dyes.
Disperse dyestuffs containing cyanomethyl ester groups are known from literature and are described for example in GB 909,843, DE-A 2130992, GB 1 ,457,532, GB 1 ,536,429, FR-A 1 ,531 , 147, US 3,776,898, JP 551 61 857, GB 2, 1 04,088, EP 0 685 531 A1 and WO 95/20014.
The inventor of the present invention has surprisingly found that dyeings on polyester with very good wet fastness properties can be obtained if selected dyestuffs containing one cyanomethylester group as defined below are used.
The present invention claims dyestuffs of the formula I
wherein
D is a group of the formula (Ha)
wherein T\ T2 and T3 are, independently, hydrogen, halogen or nitro; T4 is hydrogen, halogen, cyano or nitro; wherein at least one of T\ T2, T3 and T4 is not hydrogen; or a group of the formula (lib)
wherein T5 is hydrogen or halogen; and T6 is hydrogen -SO2CH3, -SCN or nitro; wherein at least one of T5 and T6 is not hydrogen; or a group of the formula (lie)
or a group of the formula (lid)
wherein T7 is nitro, -CHO or a group of the formula
T is -H, halogen, nitro and cyano; T8 is hydrogen or halogen; and T9 is nitro, cyano, -COCH3 or -COOT10, wherein T10 is (C,-C4)-alkyl; or a group of the formula (lie)
R1 is hydrogen, (C C4)-alkyl or -NCOR6, where R6 is (C,-C4)-alkyl or phenyl;
R2 is unsubstituted (C,-C6)-alkyl, substituted (C C6)-alkyl, benzyl or phenylethyl; R3 is hydrogen or methyl; R4 is hydrogen or methyl; R5 is hydrogen, methyl or phenyl; R7 is hydrogen, chloro, methoxy or ethoxy; n is 0, 1 or 2; s is 0 or 1 ;
with the proviso that in the case R1, R3, R4, R5 and R7 are hydrogen and n = 0
D is a group of the formula (lie), (lid), (lie) or (lla) wherein T1 is not nitro if T2, T3 and T4 are hydrogen, - if T2 and T3 are hydrogen and T4 is chlorine or cyano and if T2 and T4 are hydrogen and T3 is chlorine; and
with the further proviso that
R2 is unsubstituted (C C6)-alkyl if R1 is methyl, R3, R4, R5 and R7 are hydrogen and n = 0.
Alkyl groups standing for R1, R6 or T10 may be straight-chain or branched and are preferably methyl, ethyl, n-propyl, i-propyl or n-butyl. The same applies to alkyl groups standing for R2, which can in addition be pentyl or hexyl. Substituted alkyl groups standing for R2 are preferably substituted by hydroxyl, (C C4)-alkoxy or halogen. Halogen standing for T\ T2, T3, T4, T5 or T8 are preferably chlorine or bromine.
Preferred examples for D derive from the following amines: 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-chloro-4-nitroaniline, 4-chloro-2- nitroaniline, 2-bromo-4-nitroaniIine, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4- nitroaniline, 2-ch oro-6-bromo-4-nitroaniline, 2,5-dichloro-4-nitroaniline, 2-cyano- 4-nitroaniline, 2-cyano-6-bromo-4-nitroaniline, 2-cyano-6-ch!oro-4-nitroaniline, 2,4-dinitroaniIine, 2-chloro-4,6-dinitroaniIine, 2-bromo-4,6-dinitroaniline, 2,6- dicyano-4-nitroaniIine, 2-cyano-4,6-dinitroaniline, 2-amino-5-nitrothiazole, 2- amino-3,5-dinitrothiophene, 2-amino-3-ethoxycarbonyl-5-nitrothiophene, 2- amino-3-acetyl-5-nitrothiophene, 2-amino-3-cyano-5-nitrothiophene, 2-amino-3- cyano-4-chloro-5-formylthiophene, 7-amino-5-nitrobenzoisothiazole, 2-amino-6- nitrobenzothiazole, 2-amino-6-methylsulphonylbenzothiazole; 2-amino-6- thiocyanatobenzothiazole, 2-amino-5,6-dichlorobenzothiazole and 2-amino-6,7- dichlorobenzothiazole (mixture). 5 Preferred disperse dyestuffs according to the present invention are of the general formula (la)
wherein 10 D is a group of the formulae (Ha), (lib), (lie), (lid) or (lie); R1 is (C C4)-alkyl; R2 is unsubstituted (C C6)-alkyl, benzyl or phenylethyl; and n is 0, 1 or 2.
15 In especially preferred dyestuffs of formula (la) R1 is methyl, R2 is ethyl and n is 0.
Other preferred disperse dyestuffs according to the present invention are of the general formula (lb)
\} wherein T3 is bromo or chloro; and R2 is unsubstituted (C C6)-alkyl, substituted (C C6)-alkyl, benzyl or phenylethyl; 25 In especially preferred dyestuffs of formula (lb) R2 is ethyl, benzyl or phenethyl. Still other preferred disperse dyestuffs according to the present invention are of the general formula (lc)
wherein D is a group of the formulae (lla), (lib), (lie), (ild) or (lie);
R1 is hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (CrC4)-alkyl or phenyl;
R2 is unsubstituted (CrC6)-alkyl, substituted (CrC6)-alkyI, benzyl or phenylethyl; and
R3 is hydrogen and R is methyl or R3 is methyl and R is hydrogen.
Still other preferred disperse dyestuffs according to the present invention are of the general formula (Id)
wherein D is a group of the formulae (lla), (lib), (lie), (Ild) or (lie);
R1 is hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (C C4) -alkyl or phenyl;
R2 is unsubstituted (C C6)-alkyl, substituted (C C6) -al yl, benzyl or phenylethyl; and
R5 is methyl or phenyl;
Still other preferred disperse dyestuffs according to the present invention are of the general formula (le)
wherein
D is a group of the formulae (lla), (lib), (lie), (Ild) or (lie);
R2 is unsubstituted (C C6)-alkyl, substituted (CrC6)-alkyl, benzyl or phenylethyl; R6 is (CrC4)-aIkyl or phenyl;
R7 is chloro, methoxy or ethoxy; and n is 0, 1 or 2.
Still other preferred disperse dyestuffs according to the present invention are of the general formula (If)
wherein
R2 is unsubstituted (C C6)-aikyl, substituted (C C6)-alkyl, benzyl or phenylethyl; R8 is nitro; and n is 0, 1 or 2;
Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ig)
wherein
D is a group of the formulae (lla), (Mb), (He), (lid) or (lie);
R1 is hydrogen, (C C4)-alkyi or -NCOR6, where R6 is (CrC4)-alkyi or phenyl;
R2 is unsubstituted (C,-C6)-alkyl, substituted (C C6)-alkyl, benzyl or phenylethyl; and R3 is hydrogen or methyl. The compounds of the formula I may be obtained by usual methods for the preparation of azo compounds such as by diazbtisation of an amine of the formula III D-NH2 (III) wherein D is defined as given above, and coupling onto a compound of the formula IV
wherein R\ R2, R3, R4, R5 and R7 are defined as given above.
Typically the amine of the formula (III) may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from -1 0°C to 1 0°C. Coupling onto the compound of the formula (IV) may be achieved by adding the diazotised amine to the compound of the formula (IV) under conditions described in literature and known to the skilled persons.
After coupling the compound of the formula (I) may be recovered from the reaction mixture by any convenient means such as filtration. The compounds of the formulae (III) and (IV) are known and can be obtained by methods described in literature or known to the skilled person.
The compounds of the formula (I) are useful for dyeing and printing of synthetic textile material particularly polyester textile materials and fibre blends thereof with for example cellulosic materials like cotton, to which they impart colours Y which have excellent wet fastness properties.
Dyeing of the fibre goods mentioned with the dyestuffs of the formula (I) can be carried out in a manner known per se, preferably from aqueous dispersions, if appropriate in the presence of carriers, at between 80 and 1 1 0°C, by the exhaust process or by the HT process in a dyeing autoclave at 1 1 0 to 1 40°C, and by the so-called thermofixing process, in which the goods are padded with the dye liquor and then fixed at about 1 80 to 230°C.
The fibre goods mentioned can as well be printed in a manner known pers e by a procedure in which the dyestuffs of the formula (I) are incorporated into a printing paste and the goods printed with the paste are treated , if appropriate in the presence of a carrier, with HT steam, pressurized steam or dry heat at temperatures between 180 and 230°C to fix the dyestuff.
The dyestuffs of the formula (I) should be present in the finest possible dispersion in the dye liquors and printing pastes employed in the above applications.
The fine dispersion of the dyestuffs is effected in a manner known per se by a procedure in which the dyestuff obtained during preparation is suspended ina liquid medium, preferably in water, together with dispersing agents and the mixture is exposed to the action of shearing forces, the particles originally present being comminuted mechanically to the extent that an optimum specific surface area is achieved and sedimentation of the dyestuff is as low as possible. The particle size of the dyestuffs is in general between 0.5 and 5 m, preferably about 1 m. The dispersing agents used can be nonionic or anionic. Nononic dispersing agents are, for example, reaction products of alkylene oxides, such as, for example, ethylene oxide or propyiene oxide, with alkylatable compounds, such as for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines. Anionic dispersing agnets are, for example, lignin- sulphonates, alkyl- or alkylarylsulphonates or alkylaryl polyglycol ethersulphates. For most methods of use, the dyestuff formulations thus obtained should be The dyestuff and dispersing agent content is therefore limited in these cases. In general, the dispersions are brought to a dyestuff content of up to 50 per cent by weight and a dispersing agent content of up to 25 per cent by weight. For economic reasons, the dyestuff contents usually do not fall below 1 5 per cent by weight. The dispersions can also comprise other auxiliaries, for example those which act as oxidizing agents or fungicidal agents. Such agents are well known in the art. The dyestuff dispersion thus obtained can be used very advantageously for the preparation of printing pastes and dye liquors.
For certain fields of use, powder formulations are preferred. These powders comprise the dyestuff, dispersing agents and other auxiliaries, such as, for example, wetting agents, oxidizing agents, preservatives and dust removal agents.
A preferred preparation process for pulverulent dyestuff formulations comprises removing the liquid from the liquid dyestuff dispersions described above, for example by vacuum drying, freeze drying, by drying on roller dryers, but preferably by spray drying.
Example 1
4-(4-nitrophenylazo)-3-methyl-N-ethyI-N-(2-cyanomethoxy- carbonylethyl) aniline
4-nitroaniline (4.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (50parts). Nitrosyl sulphuric acid 40% (1 1 .4parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution obtained was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyi)-m-toluidine (7.3parts), methanol (50parts), water (200parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- (4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline (6.5parts) λmax = 486nm (acetone) When applied to polyester materials from aqueous dispersion, red shades ,.§yjth excellent wet and light fastness properties were seen.
The following examples of dyes of formula (laa): were prepared by the procedure of Example 1 (see Table 1 )
Table 1
Example 65 4-(2,6-dichloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxy- carbonylethyl) aniline
2,6-dichloro-4-nitroaniline (6.2parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:1 (40parts). Nitrosyl sulphuric acid 40% (1 1 .4parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2(cyanomethoxycarbonylethyl)-aniline (8.3parts), methanol (50parts), water (300parts) and sulphamic acid O part). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(2,6-dichloro-4- nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline (9.5parts) λmax = 432nm (acetone)
When applied to polyester materials from aqueous dispersion, yellow brown shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iba)
were prepared by the procedure of Example 65 (see Table 2)
Table 2
Example 80 4-(6-nitrobenzothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline
2-amino-6-nitrobenzothiazole (3.9parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (40parts). Nitrosyl sulrlhuric acid 40% (7.6parts) was added below 5°C and the mixture was stirred for 1 hour. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (5.9parts), methanol (25parts), water (200parts) and sulphamic acid (0.5parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(6-nitrobenzothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonyl ethyl) aniline (2.4parts) λmax = 545nm (acetone)
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (lab):
were prepared by the procedure of Example 80 (see Table 3)
Table 3
Example 1 07 4-(3,5-dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline
2-amino-3,5-dinitrothiophene (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (50parts) . Nitrosyl sulphuric acid 40% (5.7parts) was added below 5°C and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonyethyl)-m-toluidine (4.0parts), acetone (50parts), water (300parts) and sulphamic acid (O.δparts) . After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(3,5- dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonyl- ethyl) aniline (3.0parts) λmax = 640nm (acetone) When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (lac):
were prepared by the procedure of Example 107 (see Table 4)
Table 4
Example 1 27 4-(5-nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N-(2- cyanomethoxycarbonyiethyl) aniline
7-amino-5-nitrobenzoisothiazole (2.9parts) was added to a mixture of sulphuric acid 98% (1 5parts) and phosphoric acid (4parts) stirring at room temperature. The mixture was heated to 55°C and was stirred at that temperature for 30mins. Nitrosyl sulphuric acid 40% (6.1 parts) was added below 5°C and the mixture was stirred for 2hrs. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (4.8parts), acetone (50parts), water O OOparts) and sulphamic acid (O.δparts). Sodium acetate was added to increase the pH to 4.0 and the mixture was stirred for 1 hour. The product was isolated by filtration, washed with cold water apd dried to yield, 4-(5- nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N -f -cyanomethoxycarbonylethyl) aniline (2.4parts) λmax = 601 nm (acetone) When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen. The following examples of dyes of Formula (lad)
were prepared by the procedure of Example 1 27 (see Table 5)
Table 5
Example 134
4-(5-nitrothiazol-yl-azo)-N-butyl-N-(2-cyanomethoxy- carbonylethyl) aniline
2-amino-5-nitrothiazole (2.9parts) was was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (50parts). Nitrosyl sulphuric acid 40% (7.0parts) was added below 5°C and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-butyl, N-2(cyanomethoxycarbonylethyl)-aniline (δ.2parts), acetone (δOparts), water (200parts) and sulphamic acid (O.δparts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(δ- nitrothiazol-yl-azo)-N-butyl-N-(2-cyanomethoxycarbonylethyl) aniline (2.9parts) λmax = 671 nm (acetone)
When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (lae)
were prepared by the procedure of Example 134 (see Table 6)
Table 6
Example 1 39 4 (2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2- cyanomethoxycarbonylethyD-aniline
2-chloro-4-nitroaniline (3.δparts) was set stirring at δ°C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (7.0parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of 3(N- ethyl, N-cyanomethoxycarbonylethyl)-amino-acetanilide (6.3parts), methanol (40parts), water (200parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- (2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2-cyanomethoxy- carbonylethyD-aniline (4.1 parts) λmax = 52δnm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of formula (lea):
were prepared by the procedure of Example139 (see Table 7)
Table 7
Example 1 67 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(4- cyanomethoxycarbonylbutyD-aniline
2-cyano-4-nitroaniline (3.2part,s) was set stirring at δ°C with a mixture of acetic acid and propionic acid, 86:14s(δ0parts). Nitrosyl sulphuric acid 40% (7.6parts) was added below δ°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(4-cyanomethoxycarbonylbutyl)-m-toluidine (δ.Oparts), methanol (δOparts), water (200parts) and sulphamic acid part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4- nitrophenylazo)-3-methyl-N-ethyl-N-(4-cyanomethoxycarbonyl butyD-aniline. (δ.3parts) λmax = 648nm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (laf)
were prepared by the procedure of Example167 (see Table 8) Table 8
Example 1 69 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1 -cyanoethoxy) carbonylethyD-aniline
2-cyano-4-nitroaniline (2.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (40parts). Nitrosyl sulphuric acid 40% (4.9parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1 -cyanoethoxy)carbonylethyl)-m-toluidine (3.7parts), acetone (δOparts), water (300parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4- nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1 -cyanoethoxy) carbonylethyD-aniline (3.5parts) λmax = 534nm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ida
were prepared by the procedure of Example169 (see Table 9)
Table 9
Example 194 4-(2-chloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxy carbonylpropyD-aniline
2-chloro-4-nitrόa;hiline (parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (40parts). Nitrosyl sulphuric acid 40% (4.9parts) was added below δ°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2-(cyanomethoxycarbonylpropyl)-aniline (parts), acetone (δOparts), water (300parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-chloro-4- nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylpropyl)-aniline (3.δparts) λmax = 634nm (acetone) When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (lea)
were prepared by the procedure of Example194 (see Table 10)
Tablel O
Example 21 3 4-(4-nitrophenylazo)-N-ethyl-N-(2-( 1 -cyanoethoxy) carbonylpropyD-aniline
4-nitroaniline (2.0parts) was set stirring at δ°C with a mixture of acetic acid and propionic acid, 86: 14 (δOparts). Nitrosyl sulphuric acid 40% (δ.7parts) was added below δ°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1 -cyanoethoxy)carbonylpropyl)-aniline (4.7parts), acetone (δOparts), water (200parts) and sulphamic acid O part) . After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(4-nitrophenylazo)-N- ethyl-N-(2-(1 -cyanoethoxy)carbonylpropyl)-aniline (2.9parts) λmax = 473nm (acetone) When applied to polyester materials from aqueous dispersion, scarlet shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ih):
were prepared by the procedure of Example 21 3 (see Table 1 X Table 1 1
Example 226
4-(2-cyano-4-nitrophenylazo)-N-ethyl-N-(1 -cyanomethoxy carbonylethyl)-m- toluidine
2-cyano-4-nitroaniline (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (40parts). Nitrosyl sulphuric acid 40% (6.6parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-0 -cyanomethoxycarbonylethyl)-m-toluidine (4.1 parts), methanol (40parts), water (200parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4- nitrophenylazo)-N-ethyl-N-(1 -cyanomethoxycarbonylethyl)-m-toluidine (3.9parts) λmax = 61 0nm (acetone) When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.

Claims

Patent Claims
1 . Dyestuff of the formula I
wherein D is a group of the formula (lla)
wherein T1 , T2 and T3 are, independently, hydrogen, halogen or nitro; T4 is hydrogen, halogen, cyano or nitro; wherein at least one of T\ T2, T3 and T4 is not hydrogen; or a group of the formula (lib)
wherein T5 is hydrogen or halogen; and T6 is hydrogen -SO2CH3, -SCN or nitro; wherein at least one of T5 and T6 is not hydrogen; or a group of the formula (lie)
or a group of the formula (Ild) wherein T7 is nitro, -CHO or a group of the formula wherein T10 is -H, halogen, nitro and cyano; T8 is hydrogen or halogen; and T9 is nitro, cyano, -COCH3 or -COOT10, wherein T10 is (CrC4)-alkyl; or a group of the formula (lie)
R1 s hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (C C4)-alkyl or phenyl; R2 s unsubstituted (C,-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl;
R3 s hydrogen or methyl; R4 s hydrogen or methyl; R5 s hydrogen, methyl or phenyl; R7 s hydrogen, chloro, methoxy or ethoxy; n is 0, 1 or 2; s is 0 or 1 ;
with the proviso that in the case R1, R3, R4, R5 and R7 are hydrogen and n = 0
D is a group of the formula (He), (Ild), (He) or (lla) wherein T1 is not nitro if T2, !•? and T4 are hydrogen, if T2 anU T3 are hydrogen and T4 is chlorine or cyano and if T2 and T4 are hydrogen and T3 is chlorine; and
with the further proviso that
R2 is unsubstituted (CrC6)-alkyl if R1 is methyl, R3, R4, R5 and R7 are hydrogen and n = 0.
2. Dyestuff according to claim 1 of the formula (la)
wherein
D is a group of the formulae (lla), (lib), (He), (Ild) or (We); R1 is (C rC4) -alkyl ;
R2 is unsubstituted (C,-C6)-alkyl, benzyl or phenylethyl; and n is 0, 1 or 2.
3. Dyestuff according to claim 1 of the formula (lb)
wherein T3 is bromo or chloro; and
R2 is unsubstituted (C,-C6)-alkyl, substituted (C,-C6)-alkyl, benzyl or phenylethyl;
4. Dyestuff according to claiml of the formula (lc)
wherein
D is a group of the formulae (lla), (lib), (lie), (Ild) or (We);
R1 is hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (CrC4)-alkyl or phenyl;
R2 is unsubstituted (C.,-Cβ)-alkyl, substituted (C^CeJ-alkyl, benzyl or phenylethyl; and R3 is hydrogen and R4 is methyl or R3 is methyl and R is hydrogen. δ. Dyestuff according to claiml of the formula (Id)
wherein
D is a group of the formulae (Ha), (lib), (He), (Ild) or (lie); R1 is hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (CrC4)-alkyl or phenyl; R2 is unsubstituted (C,-C6)-alkyl, substituted (C,-C6)-alkyl, benzyl or phenylethyl; and R5 is methyl or phenyl;
6. Dyestuff according to claim l of the formula (le)
wherein D is a group of the formulae (lla), (lib), (lie), (Ild) or (We);
R2 is unsubstituted (CrC6)-alkyl, substituted (C C6)-alkyl, benzyl or phenylethyl;
R6 is (CrC4)-alkyl or phenyl;
R7 is chloro, methoxy or ethoxy; and n is 0, 1 or 2.
7. Dyestuff according to claiml of the formula (If)
wherein R2 is unsubstituted (CrC6)-alkyl, substituted (CrC6)-alkyl, benzyl or phenylethyl; R8 is nitro; and n is 0, 1 or 2;
8. Dyestuff according to claiml of the formula (Ig)
wherein
D is a group of the formulae (lla), (lib), (He), (Ild) or (We); R1 is hydrogen, (C C4)-alkyl or -NCOR6, where R6 is (C C4)-alkyl or phenyl; R2 is unsubstituted (C,-C6)-alkyl, substituted (C^C^-alky!, benzyl or phenylethyl; and R3 is hydrogen or methyl.
9. Process for the preparation of a dyestuff as claimed in one or more of claims 1 to 8, which comprises diazotisation of an amine of the formula III D-NH2 (III) wherein D is defined as given in the preceding claims, and coupling onto a compound of the formula IV
wherein R1, R2, R3, R4, R5 and R7 are defined as given in the preceding claims.
1 0. The use of a dyestuff as claimed in one or more of claims 1 to 8 for dyeing and printing of synthetic textile material and fibre blends thereof.
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PT1678259T (en) 2016-11-21
GB0324584D0 (en) 2003-11-26
TWI408176B (en) 2013-09-11
RU2376334C2 (en) 2009-12-20
HK1093351A1 (en) 2007-03-02
WO2005040283A3 (en) 2005-06-30
CN1871306A (en) 2006-11-29
ES2611945T3 (en) 2017-05-11
KR20060123719A (en) 2006-12-04
JP2007509214A (en) 2007-04-12
BRPI0415469A (en) 2006-12-19
CN100439450C (en) 2008-12-03
TW200523322A (en) 2005-07-16
RU2006116739A (en) 2007-11-27
CA2543056A1 (en) 2005-05-06
MXPA06002919A (en) 2006-05-31
US7358345B2 (en) 2008-04-15
EP1678259B1 (en) 2016-08-17
WO2005040283A2 (en) 2005-05-06
KR101141572B1 (en) 2012-05-03
US20070050928A1 (en) 2007-03-08

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